CN109734106A - A method of high concentration solution of sodium bisulfite is prepared using trade waste - Google Patents
A method of high concentration solution of sodium bisulfite is prepared using trade waste Download PDFInfo
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Abstract
A method of high concentration solution of sodium bisulfite being prepared using trade waste, calcium sulfite is added to the water by (1), and stirring is made into the suspension that concentration is 20-35%；(2) saltcake is added after adjusting sulfuric acid concentration to 3-3.5mol/L；(3) at 20-30 DEG C, the solution of step (2) is added dropwise into calcium sulfite suspension, 30-60min is stirred to react, filtered through filters pressing or decompression and obtain solution of sodium bisulfite；(4) calcium sulfite is continuously added in the solution of sodium bisulfite made from step (3), is configured to calcium sulfite concentration and is the suspension of 20-30%, then reacted with same condition, obtains solution of sodium bisulfite.The present invention has recycled chlorine industry waste and desulfurization intermediate product calcium sulfite is transformed into the higher sodium hydrogensulfite of added value, and the technique for also simplifying smoke-gas wet desulfurization also solves the energy consumption problem that sodium sulfite evaporating, concentrating and crystallizing faces.
Description
Technical field
The invention belongs to environmental protection and inorganic salts preparation fields, and in particular to a kind of sub- using trade waste preparation high concentration
The method of sodium bisulfate.
Background technique
Using film filtering low-temperature denitration method to the raw material salt of electrolysis production caustic soda refine it is pretreated during
Saltcake can be generated, yield is about 100,000 tons of saltcake/1,000,000 ton caustic soda, and the saltcake purity is up to 99% or so.In addition, sewage
The freezing denitrification process of the salt lake for the treatment of industry and western China industry can also generate a large amount of saltcake.Since saltcake is readily soluble
The features such as Yu Shui, water content are big, surcharge is low, market capacity is limited leads to dealing carefully with and utilizing as related for saltcake
The intractable problem of enterprise.
Chlorine industry can generate the Waste Sulfuric Acid of 60-70% during vinyl chloride dry using the concentrated sulfuric acid.Part copper smelting
Recovery processing sulfur dioxide can also generate a large amount of sulfuric acid in refining production process, utilize and processing is also as the negative of relevant enterprise
Load.
The production of chlor-alkali industry especially calcium carbide needs a large amount of electric energy, and statistics shows that one ton of calcium carbide needs about 3300 degree of electricity
Energy.Gu Lvjianshengchanchang is generally close to power plant.With the raising of environmental protection standard and the reinforcement of law enforcement dynamics, to titanium dioxide in flue gas
The improvement of sulphur has been enforced.The prevailing technology of coal fired power plant flue gas desulfurization is wet process limestone/lime-gypsum at present,
Technique mainly includes that sulfur dioxide absorbs generation calcium sulfite precipitating and two step of calcium sulfite oxidation, wherein first step sulfur dioxide
The reaction speed for absorbing generation calcium sulfite suspension is very fast；Second step reaction speed is slower, needs to utilize high-power blower drum
Calcium sulfite could be forced by repeatedly circulation to be oxidized to calcium sulfate by entering large quantity of air, consume a large amount of electric energy.If by two
The improvement reaction of sulfur oxide, which rests on, generates the calcium sulfite stage, can not only save a large amount of electric energy of oxidation section, can be with
Sulphite is produced using the inferior sulfate radical that calcium sulfite contains, has the characteristics that energy conservation and environmental protection, resource reutilization.
Sodium hydrogensulfite is the chemical reagent that a kind of purposes is wide, dosage is big, is widely used in cotton fabric and organic matter
Bleaching is used as reducing agent in dyestuff, papermaking, process hides, chemical synthesis industry, for producing intermediate in medical industry.Food
It is used as bleaching agent, preservative and antioxidant etc. with grade product.Production method industrial at present is to be produced using sulphur or troilite
Raw sulfur dioxide, which is passed through in aqueous slkali, generates sodium hydrogensulfite, haves the defects that technique is more complex, at high cost.
Sulphite is produced using saltcake also more report.The former Soviet Union was studied early in the 1940s with regard to someone
With saltcake, lime and sulfur dioxide sodium hydrogensulfite.The patent that Lu Jianyuan etc. is declared is " a kind of to produce lightweight two with sodium sulphate method
The technique of silica and sodium sulfite " (200680019143.0) is provided to be produced at high temperature using sodium sulphate and quartz sand and charcoal
Sodium silicate solid and sulfur dioxide dissolve sodium silicate solid to obtain sodium silicate solution, then react with sulfur dioxide and generate lightweight
Silica and sodium sulfite, reaction process condition are harsh；Patent " a kind of regeneration of accumulator desulfurating agent that Shao Chunyan etc. is declared
The method that method " (CN97105109.7) provides is that sodium sulphate and calcium sulfite and sulfuric acid reaction are generated gypsum and bisulfite
Sodium, then sodium hydrogensulfite and lime reaction are generated into calcium sulfite and sodium hydroxide, it is raw that carbon dioxide is passed through into sodium hydroxide
Circulation desulfurization agent is obtained at sodium carbonate.But the concentration of sodium bisulphite that the reaction generates is lower, brings processing work for later use
Skill and the deficiency that energy consumption is high.
Summary of the invention
It is an object of that present invention to provide it is a kind of using trade waste preparation high concentration solution of sodium bisulfite method, with
The waste saltcake and Waste Sulfuric Acid and smoke-gas wet desulfurization intermediate product calcium sulfite of chlorine industry are as raw material, by twice
Metathesis reaction generates high concentration solution of sodium bisulfite, and the present invention has been recycled and produced among chlorine industry waste and desulfurization
Object calcium sulfite is transformed into the higher sodium hydrogensulfite of added value, in addition, the technique of smoke-gas wet desulfurization is also simplified, while
Solves the energy consumption problem that sodium sulfite evaporating, concentrating and crystallizing faces.
The technical solution adopted by the present invention is that:
A method of high concentration solution of sodium bisulfite is prepared using trade waste, comprising the following steps:
(1) calcium sulfite is added to the water, stirring is made into the suspension that concentration is 20-35%；
(2) sulfuric acid concentration is adjusted to 3-3.5mol/L, saltcake is dissolved in the sulfuric acid solution for adjusting concentration；
(3) at 20-30 DEG C, sulfurous acid will be added by the way of being added dropwise dissolved with the sulfuric acid solution of saltcake in step (2)
In calcium suspension, stirred with the revolving speed of 60-120r/min, stop reaction after the 30-60min that drips that the reaction was continued, through filters pressing or
Decompression filters and obtains solution of sodium bisulfite, and concentration about 170-190g/L, calcium sulfite conversion ratio is in 90-95%；
(4) calcium sulfite is continuously added in the solution of sodium bisulfite made from step (3), is configured to calcium sulfite concentration
Continue the sulfuric acid solution in a dropping step (2) dissolved with saltcake, then at 20-30 DEG C for the suspension of 20-30% with 60-
The stirring of 120r/min revolving speed stops reaction after the 30-60min that drips that the reaction was continued, filters through filters pressing or decompression and obtain sulfurous acid
Hydrogen sodium solution, concentration about 270-290g/L, is close to or up to saturated concentration, brings convenience for subsequent applications with processing.
Further, in step (3) and step (4) two-step reaction, the molar ratio of each reactant are as follows: calcium sulfite, sulfuric acid
The 1:1.1:1 of sodium, sulfuric acid, wherein saltcake (sodium sulphate) excessive 10%, it is therefore an objective to improve the conversion ratio of other two reactants.
Further, step (4) preparation solution of sodium bisulfite can be used directly, or through pervaporation, cooling, crystallization,
Sodium hydrogensulfite solid is made in the processes such as dry.
Further, the gypsum generated after step (4) reaction, prepares semi-hydrated gypsum or nothing after washing, drying, calcining
Water gypsum.
Beneficial effects of the present invention:
The present invention is led to using chlorine industry waste saltcake and Waste Sulfuric Acid and flue gas desulfurization intermediate product calcium sulfite as raw material
The solution of sodium bisulfite for crossing 2 room temperature solid-liquid reaction preparation high concentrations, has environmental protection, energy conservation, simple process, efficient, cost
Low, convenient feature, in addition, by the reactant that low price is added, the conversion ratio for high or rich content substance of improving price,
It increases economic efficiency.
Reaction equation is as follows:
2CaSO3+Na2SO4+H2SO4=2NaHSO3+2CaSO4↓
Cause to decompose because acidity is excessively high to prevent desulfurization product calcium sulfite from meeting sulfuric acid, be first made into water using calcium sulfite
Then the mode of saltcake and sulfuric acid mixed solution is added dropwise in high density slurry again, generate gypsum and sodium hydrogensulfite.It meanwhile being drop
The solution of sodium bisulfite that first time generates is made into calcium sulfite by the energy consumption of low subsequent sodium hydrogensulfite recycling, invention again
Slurry is reacted, and after two secondary responses, 270-290g/L is can be improved in the concentration of sodium hydrogensulfite, is close to or up to full
And concentration.This provides convenience for subsequent evaporating, concentrating and crystallizing, saves plenty of time and the energy.
Specific embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
Calcium sulfite and water stirring are made into the suspension that concentration is 30% in first set reaction, sulfuric acid concentration is adjusted to
Saltcake is dissolved in sulfuric acid solution by 3mol/L.Controlling reaction temperature is 20 DEG C, will be added dropwise dissolved with the sulfuric acid solution of saltcake into Asia
In suspension of calcium sulfate, with the stirring of 100r/min revolving speed, stops reaction after the 30min that drips that the reaction was continued, obtain Asia through filters pressing
Sodium bisulfate, concentration about 180g/L, calcium sulfite conversion ratio is 92%.
Calcium sulfite suspension, concentration 30% are prepared with second of this solution of sodium bisulfite, sulfuric acid concentration control is
3mol/L, control reaction temperature are 20 DEG C, will be added in calcium sulfite suspension dissolved with the sulfuric acid solution of saltcake, with 100r/min
Revolving speed stirring stops reaction after the 30min that drips that the reaction was continued, obtains solution of sodium bisulfite, concentration about 280g/L through filters pressing.
It can be used directly, or sodium hydrogensulfite solid is made through processes such as pervaporation, cooling, crystallization, dryings.The gypsum generated is recycled,
Semi-hydrated gypsum or anhydrous gypsum are prepared after washing, drying, calcining.
Embodiment 2
Calcium sulfite and water stirring are made into the suspension that concentration is 20% in first set reaction, sulfuric acid concentration control is
Saltcake is dissolved in sulfuric acid solution by 3.5mol/L.Control reaction temperature be 20 DEG C, by dissolved with the sulfuric acid solution of saltcake be added dropwise into
In calcium sulfite suspension, with the stirring of 100r/min revolving speed, stops reaction after the 30min that drips that the reaction was continued, filtered through decompression
Solution of sodium bisulfite is obtained, concentration about 170g/L, calcium sulfite conversion ratio is 94%.
Calcium sulfite suspension, concentration 20% are prepared with second of this solution of sodium bisulfite, sulfuric acid concentration control is
3.5mol/L, control reaction temperature are 20 DEG C, will be added dropwise dissolved with the sulfuric acid solution of saltcake into calcium sulfite suspension, with
The stirring of 100r/min revolving speed stops reaction after the 30min that drips that the reaction was continued, filters through decompression and obtain solution of sodium bisulfite,
Concentration about 270g/L.It can be used directly, or sodium hydrogensulfite solid is made through processes such as pervaporation, cooling, crystallization, dryings.It returns
Midwifery at gypsum, semi-hydrated gypsum or anhydrous gypsum are prepared after washing, drying, calcining.
Embodiment 3
Calcium sulfite and water stirring are made into the suspension that concentration is 35% in first set reaction, sulfuric acid concentration control is
Saltcake is dissolved in sulfuric acid solution by 3mol/L.Controlling reaction temperature is 20 DEG C, will be added dropwise dissolved with the sulfuric acid solution of saltcake into Asia
In suspension of calcium sulfate, with the stirring of 100r/min revolving speed, stops reaction after the 30min that drips that the reaction was continued, filtered through decompression
To solution of sodium bisulfite, concentration about 190g/L, calcium sulfite conversion ratio is 90%.
Calcium sulfite suspension, concentration 35% are prepared with second of this solution of sodium bisulfite, sulfuric acid concentration control is
3mol/L, control reaction temperature are 20 DEG C, will be added dropwise dissolved with the sulfuric acid solution of saltcake into calcium sulfite suspension, with 100r/
The stirring of min revolving speed stops reaction after the 30min that drips that the reaction was continued, filters through decompression and obtain solution of sodium bisulfite, concentration is about
290g/L.It can be used directly, or sodium hydrogensulfite solid is made through processes such as pervaporation, cooling, crystallization, dryings.Recycling generates
Gypsum, semi-hydrated gypsum or anhydrous gypsum are prepared after washing, drying, calcining.
Claims (4)
1. a kind of method using trade waste preparation high concentration solution of sodium bisulfite, which is characterized in that including following step
It is rapid:
(1) calcium sulfite is added to the water, stirring is made into the suspension that concentration is 20-35%；
(2) sulfuric acid concentration is adjusted to 3-3.5mol/L, saltcake is dissolved in the sulfuric acid solution for adjusting concentration；
(3) at 20-30 DEG C, by being added by the way of being added dropwise in step (2) dissolved with the sulfuric acid solution of saltcake, calcium sulfite is outstanding
It in supernatant liquid, is stirred with the revolving speed of 60-120r/min, stops reaction after the 30-60min that drips that the reaction was continued, through filters pressing or decompression
Suction filtration obtains solution of sodium bisulfite；
(4) calcium sulfite is continuously added in the solution of sodium bisulfite made from step (3), being configured to calcium sulfite concentration is
The suspension of 20-30% continues the sulfuric acid solution in a dropping step (2) dissolved with saltcake, then at 20-30 DEG C with 60-
The stirring of 120r/min revolving speed stops reaction after the 30-60min that drips that the reaction was continued, filters through filters pressing or decompression and obtain sulfurous acid
Hydrogen sodium solution.
2. a kind of method using trade waste preparation high concentration solution of sodium bisulfite as described in claim 1, special
Sign is, in step (3) and step (4) two-step reaction, the molar ratio of each reactant are as follows: calcium sulfite, sodium sulphate, sulfuric acid 1:
1.1:1.
3. a kind of method using trade waste preparation high concentration solution of sodium bisulfite as described in claim 1, special
Sign is that the solution of sodium bisulfite of step (4) preparation can be used directly, or through processes such as pervaporation, cooling, crystallization, dryings
Sodium hydrogensulfite solid is made.
4. a kind of method using trade waste preparation high concentration solution of sodium bisulfite as described in claim 1, special
Sign is that the gypsum generated after step (4) reaction prepares semi-hydrated gypsum or anhydrous gypsum after washing, drying, calcining.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975613A (en) * | 2019-12-04 | 2020-04-10 | 沈阳环境科学研究院 | Regeneration method of sodium-alkali desulfurizing agent |
| CN117004381A (en) * | 2023-06-30 | 2023-11-07 | 西安石油大学 | Salt-resistant and temperature-resistant oilfield fracturing fluid thickener |
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| CN101676205A (en) * | 2008-09-18 | 2010-03-24 | 朱作远 | Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method |
| CN106219577A (en) * | 2016-08-09 | 2016-12-14 | 石河子大学 | A kind of method utilizing smoke-gas wet desulfurization intermediate product calcium sulfite to prepare sodium sulfite |
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| CN1165114A (en) * | 1997-02-25 | 1997-11-19 | 沈阳环境科学研究所 | Regeneration method for storage battery desulfurizing agent |
| CN101676205A (en) * | 2008-09-18 | 2010-03-24 | 朱作远 | Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975613A (en) * | 2019-12-04 | 2020-04-10 | 沈阳环境科学研究院 | Regeneration method of sodium-alkali desulfurizing agent |
| CN117004381A (en) * | 2023-06-30 | 2023-11-07 | 西安石油大学 | Salt-resistant and temperature-resistant oilfield fracturing fluid thickener |
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Effective date of registration: 20230412 Address after: No. 211-2-35, Block B, Fruits and Vegetables Building, 19-3 Beisan East Road, Development Zone, Shihezi City, Xinjiang Uygur Autonomous Region, 832000 Patentee after: Shihezi Huicheng Technology Service Co.,Ltd. Address before: 832003 North four road, Shihezi, the Xinjiang Uygur Autonomous Region 221 Patentee before: SHIHEZI University |
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